Experiment 19

A Comparison of Two Different Methods for

Determination of a Rate Constant

S.H.M.C.S.Herath

164517

2018.06.04
Date : 04/06/2018

Experiment Number : 19

Experiment Title : A Comparison of two different methods for determination of a rate constant

Objectives :

• To understand approaches used to estimate errors in experimental determinations.

• To appreciate repeating experiment can reduce random errors.

• To understand limitations exists in the level of accuracy & instrumental measurements.

• To appreciate that there can be flaws in the methods (Theories).

• To determine the rate constant with minimum errors by using two methods for the hydrolysis
reaction of ethyl acetate in the alkaline medium.
Theory :
In this experiment we determine the second order rate constant for the alkaline hydrolysis of ethyl acetate
using two different methods for both gathering the data and analyzing it. One method follows the reaction
by determining the concentration of hydroxide ions by titration under second order conditions, the second
method follows the reaction by monitoring the change in conductivity under pseudo first order conditions.
CH3COOCH2CH3 + OH- CH3COO- + CH3CH2OH

Under basic conditions, the hydroxide is actually used up during the reaction. The alkaline hydrolysis is
found by experiment to be first order with respect to each ester and hydroxide, i.e. second order overall.
The rate law may therefore be written:

𝑑[𝑂𝐻 − ]
- = k2[OH-][ester] (1)
𝑑𝑡

Where k2 is the second order rate constant, and [OH-] and [ester] are the concentrations of hydroxide ions
and ester.

Equation (1) can be integrated using the boundary conditions

[OH] = [OH-]0 and [ester] = [ester]0 when t = 0 to give:

1 [𝑂𝐻 − ]0 [𝑒𝑠𝑡𝑒𝑟]
K2t= 𝑙𝑛 (2)
[𝑒𝑠𝑡𝑒𝑟]0 −[𝑂𝐻 − ]0 [𝑒𝑠𝑡𝑒𝑟]0 −[𝑂𝐻 − ]

This equation is rather cumbersome to use in practice. Especially since there are two much easier ways of
finding second order rate constants.
Case 1 : equal concentrations of reagents

If the initial concentrations of the ester and hydroxide are equal, then since one mole of ester reacts with
one mole of hydroxide, their concentrations remain equal for all times:
[ester] = [OH-]. The rate law, equation (1), then simplifies to:
𝑑[𝑂𝐻 − ]
- = k2[OH-]2 (3)
𝑑𝑡

Integrating this rate law using same boundary condition as before, [OH-] = [OH-]0

when t=0, gives:

[𝑂𝐻− ]
[𝑂𝐻− ] 𝑡
∫ − = ∫ 𝑘2 𝑑𝑡
[𝑂𝐻− ] [𝑂𝐻− ]2 0

Hence,

(4)

A plot of 1/[OH-] against t will therefore give a straight line with gradient k2.

Case 2: one reagent in excess

If the concentration of the ester say, is much greater than the concentration of the hydroxide (by at least a
factor of 100) then it remains effectively constant as the hydroxide is used up during the reaction. These are
pseudo first order conditions since the rate law now simplifies to:
-
𝑑[𝑂𝐻 − ]
- = k1[OH-]
𝑑𝑡

Where k1, is now a pseudo first order rate constant:

k1 = k2[ester]

This rate law can be integrated using the boundary condition [OH-] = [OH-]0 when t = 0:

[𝑂𝐻− ]
[𝑂𝐻− ] 𝑡
∫ − = ∫ 𝑘1 𝑑𝑡
[𝑂𝐻− ] [𝑂𝐻− ]2 0

Hence,

ln[OH-] = ln[OH-]0 - k1t

Or

[OH-] = ln[OH-]0 e-k1t

During the reaction, hydroxide ions are used up and carboxylic ions are formed:

CH3COOCH2CH3 + OH⁻ → CH3COO- + CH3CH2OH

This reaction can be followed by the change in the conductance, of the reaction mixture. Conductance is
simply the reciprocal of resistance and for a solution it depends on the number of ions in solution and how
mobile they are to make use of the change in conductance. To make use of the change in conductance, we
need to find a relationship between it and the concentration of the reagents. If we assume that the
conductance at time t, G(t), is proportional to the concentration of the ions present, we can write:

G(t) = C1[OH−] + C2[AcO−] + C3[Na+] (6)

Where C1, C2 and C3 are unknown constants. During the reaction, whilst the concentration of Na+ ions
remains unchanged, for every OH- ion used up, one AcO- ion is formed. This means:

[AcO−] = [OH−]0 − [OH−]

Where [𝑂𝐻−]0 is the initial concentration of OH- ions.

Hence, the conductance, G(t) is given by:

G(t) = C1[OH ] + C2{[OH−]0 − [OH−]} + C3[Na+] (7)

At the end of the reaction, all the OH- ions have been replaced by AcO- ions so the final concentration of
AcO- ions must be equal to the initial concentration of OH- ions, [OH-]0. The conductance at this point, G∞ is
given by:

G∞ = C2[OH−]0 + C3[Na+] (8)

Subtracting (8) from (7) gives:

G(t) − G∞ = C1[OH−] + C2[OH−]0 − C2[OH−] + C3[Na+] − C2[OH−]0 − C3[Na+]

G(t) − G∞ = {C1 − C2}[OH−]

i.e. G(t) − G∞ is proportional to [OH-] and so

[OH−] = constant {G(t) − G∞} (9)

Substituting (9) into (5)

ln{G(t) − G∞} = −k1t + constant (10)

Where, the constant contains several terms, none of which depend on time.

Hence, a graph of ln{G(t) − G∞} against time should give a straight line with gradient –k1.
Measuring k by this method suffers from the problem that the value of each point plotted on the graph
depends on G∞ and so any error in this causes a systematic distortion of the straight line, in fact leading to a
curve. This can be avoided by using the Guggenheim methods outlined below.

Guggenheim’s Method:

Equation (10) can be written:

G(t) − G∞ = Ae−k1t (11)

Where A is a constant independent of t. Similarly, the conductance at time t+Δt, G (t+Δt) will be given by,
G(t+∆t) − G∞ = Ae−k1(t+∆t) (12)

Equation (12) can also be written:

G(t+∆t) − G∞ = Ae−k1te− k1∆t (13)

Subtracting (13) from (11) gives:

G(t) − G(t+∆t) = e−k1∆t[A − Ae−k1t]

But the terms in the brackets are all constant, independent of t, so we can write:
G(t) − G(t+∆t) = e−k1tconstant

or, taking logs:

ln[G(t) − G(t+∆t)] = −k1t + constant (14)

Equation (14) tells us that a plot of ln[G(t) − G(t+∆t)] against t will give a straight line with gradient –k1, the
pseudo first order rate constant. Once k1 is found the second order rate constant k2 can be calculated from:

k1 = k2[ester]0 (4)

Where [ester]0is the initial concentration of the ester which was present in excess.

The way the Guggenheim method works in practice is that readings are taken at short regular intervals and
then paired up later so that each pair is separated by the same much longer time interval, Δt.

Pre – Laboratory Questions :

(1) Systematic error is an error having a non-zero mean, so that its effect is not reduced when
observations are averaged.
Random error is an error in measurement caused by factors which vary from one measurement to
another.
Absolute error is the magnitude of the difference between the measured value and the true value.
 Relative error is the absolute error divided by the magnitude of the exact value. It is a measurement
of the uncertainty of measurement compared to the size of the measurement.

(2) a. Conductance is an expression of the ease with which electric current flows through a substance.
Conductivity is the material’s ability to conduct electricity.
Cell constant is a function of the electrodes areas, the distance between the electrodes and the
electrical field pattern between electrodes.

b. 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦 = 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒×𝑐𝑒𝑙𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

(3) Conductance = Siemens (S)
Conductivity = Siemens per meter (S m-1)

Cell constant = Per meter (m-1)

Procedure :
A 50.00 cm3 of 0.5 M and 100.00 cm3 of 0.05 M ethyl acetate was prepared in separate volumetric flasks.

Titration Method
A 10.00 cm3 of 0.05 M HCl was added in to seven labelled conical flasks and two drops of phenolphthalein
indicator was added to the seven solutions.
A 50.00 cm3 of 0.05 M ethyl acetate and a 50.00 cm3 of 0.05 M NaOH was added to separate beakers and
the temperature was maintained below 0 °C by cooling them in an ice bath. Then the two mixtures were
mixed and the stop watch was started at the midpoint of the delivery. After 2,5,10,15,20,25 and 30 minutes,
a 10.00 cm3 sample was pipetted out and was quenched the reaction by running the 10.00cm3 into the
appropriate conical flask which already contains the HCl. The acid remaining after quenching was titrated
against 0.02 M NaOH solution.

Conductance Method
A 10 cm3 of 0.005 M NaOH solution was added into a boiling tube and a 10 cm3 of 0.5 M ethyl acetate
solution was added to a beaker. The boiling tube and the beaker was added to an ice bath and the
temperature was maintained in 5 °C.
A 0.1 M KCl solution was prepared in a 100 cm3 volumetric flask and the solution was added to a beaker.
The conductivity meter was calibrated by using the 0.1 M KCl solution. The above temperature equilibrated
two solutions were mixed well and the stop watch was started at the midpoint of the delivery. The
conductance were taken in every 30s for 10 minutes.
Results :
Titration Method
Kinetic run Time/ minutes Initial volume/ cm3 Final volume/ cm3 Volume consumed/
cm3
1 2 0.00 15.50 15.50
2 5 15.50 31.50 16.00
3 10 0.00 17.00 17.00
4 15 0.00 17.60 17.60
5 20 17.70 36.10 18.40
6 25 36.30 45.30 19.00
7 30 23.50 43.00 19.50

Conductance Method
Time/ s Conductance/ mS
0 949
30 921
60 831
90 771
120 713
150 665
180 613
210 578
240 538
270 488
300 456
330 461
360 468
390 448
420 411
450 410
480 425
510 436
540 437
570 433
600 432
Calculations :

Titration Method

1st kinetic run:

Volume of 0.02 M NaOH consumed = 15.50 cm3

15.5
Therefore number of moles of NaOH = 0.02 mol × 1000 =3.10×10-4

NaOH : HCl

1 : 1

Therefore number of moles of excess 0.05 M HCl = 3.10 × 10-4 mol

10.00
Initial number of moles of HCl = 0.05 mol × 1000 =5.0×10-4 mol

Number of moles of HCl used in the reaction mixture = (5.0-3.10) × 10-4 mol

= 1.9 × 10-4 mol

Since 1:1 ratio,

Number of moles of NaOH in 10.00 cm3 of the reaction mixture = 1.9 × 10-4 mol
1.9×10−4
Therefore the number of moles in 100.00 cm3= 10.00
× 100 = 1.9 × 10−3mol

1.9×10−3
Therefore [OH-] in the reaction mixture = 100.00×10−3 =0.019mol dm-3

2nd kinetic run:

Volume of 0.02 M NaOH consumed = 16.00 cm3

16.00
Therefore number of moles of NaOH = 0.02 × 1000
=3.2×10-4 mol

NaOH : HCl

1 : 1

Therefore number of moles of excess 0.05 M HCl = 3.2 × 10-4 mol

10.00
Initial number of moles of HCl = 0.05× =5.0×10-4 mol
1000

Number of moles of HCl used in the reaction mixture = (5.0-3.2) × 10-4 mol

= 1.8 × 10-4 mol

Since 1:1 ratio,

Number of moles of NaOH in 10.00 cm3 of the reaction mixture = 1.8 × 10-4 mol

1.8×10−4
Therefore the number of moles in 100 cm3 = 10.00
× 100 = 1.8 × 10−3 mol

1.8×10−3
Therefore [OH-] in the reaction mixture = = = 0.018 mol dm-3
100.00×10−3
3rd kinetic run:

Volume of 0.02 M NaOH consumed = 17.00 cm3

17.00
Therefore number of moles of NaOH = 0.02× =3.4 × 10-4 mol
1000

NaOH : HCl

1 : 1

Therefore number of moles of excess 0.05 M HCl = 3.4 × 10-4 mol

10.00
Initial number of moles of HCl = 0.05× 1000 =5.0×10-4 mol

Number of moles of HCl used in the reaction mixture = (5.0-3.4)× 10-4 mol = 1.6 × 10-4 mol

Since 1:1 ratio,

Number of moles of NaOH in 10.00 cm3 of the reaction mixture = 1.6 × 10-4 mol

1.6×10−4
Therefore the number of moles in 100.00 cm3= 10.00
× 100 mol =1.6 × 10-3 mol

1.6×10−3
Therefore [OH-] in the reaction mixture = 100.00×10−3
= 0.016mol dm-3

4th kinetic run:

Volume of 0.02 M NaOH consumed = 17.60cm3

17.60
Therefore number of moles of NaOH = 0.02× 10.00 =3.52× 10-4 mol

NaOH : HCl

1 : 1

Therefore number of moles of excess 0.05 M HCl = 3.52 × 10-4 mol

10.00
Initial number of moles of HCl = 0.05 × =5.0×10-4 mol
1000

Number of moles of HCl used in the reaction mixture = (5.0-3.52)× 10-4 mol

= 1.48 × 10-4 mol

Since 1:1 ratio,

Number of moles of NaOH in 10.00 cm3 of the reaction mixture =1 .48 × 10-4 mol

1.48×10−4
Therefore the number of moles in 100.00 cm3 == 10.00
× 100 mol =1.48 × 10-3 mol mol

1.48×10−3
Therefore [OH-] in the reaction mixture = = 0.0148 mol dm-3
100.00×10−3
5th kinetic run:

Volume of 0.02 M NaOH consumed = 18.40 cm3

18.40
Therefore number of moles of NaOH = 0.02 × 1000
=3.68× 10-4 mol

NaOH : HCl

1 : 1

Therefore number of moles of excess 0.05 M HCl = 3.68 × 10-4 mol

10.00
Initial number of moles of HCl = 0.05× 1000 = 5.0×10-4 mol

Number of moles of HCl used in the reaction mixture = (5.0-3.68)× 10-4 mol

= 1.08 × 10-4 mol

Since 1:1 ratio,

Number of moles of NaOH in 10.00 cm3 of the reaction mixture = 1.32 × 10-4 mol

1.32×10−4
Therefore the number of moles in 100.00 cm3= 10.00
× 100 = 1.32× 10-3

1.32×10−3
Therefore [OH-] in the reaction mixture =100.00×10−3 =0.0132mol dm-3

6th kinetic run:

Volume of 0.02 M NaOH consumed = 19.00 cm3

19.00
Therefore number of moles of NaOH = 0.02 × 1000
=3.8× 10-4 mol

NaOH : HCl

1 : 1

Therefore number of moles of excess 0.05 M HCl = 3.8× 10-4 mol

Initial number of moles of HCl = 0.05

Number of moles of HCl used in the reaction mixture = (5.0-3.8)× 10-4 mol

= 1.2 × 10-4 mol

Since 1:1 ratio,

Number of moles of NaOH in 10.00 cm3 of the reaction mixture = 1.2× 10-4 mol

1.2×10−4
Therefore the number of moles in 100.00 cm3 = 10
×100=1.2× 10-3 mol

1.2×10−3
Therefore [OH-] in the reaction mixture = =0.012mol dm-3
100.00×10−3
7th kinetic run:

Volume of 0.02 M NaOH consumed = 19.5cm3

19.5
Therefore number of moles of NaOH = 0.02× 1000=3.9× 10-4 mol

NaOH : HCl

1 : 1

Therefore number of moles of excess 0.05 M HCl = 3.9 × 10-4 mol

10.00
Initial number of moles of HCl = 0.05× 1000 = 5.0×10-4 mol

Number of moles of HCl used in the reaction mixture = (5.0-3.9)× 10-4 mol

= 1.1 × 10-4 mol

Since 1:1 ratio,

Number of moles of NaOH in 10.00 cm3 of the reaction mixture = 1.1× 10-4 mol

1.1×10−4
Therefore the number of moles in 100.00 cm3 = × 100 =1.1× 10-3 mol mol
10.00

1.1×10−3
Therefore [OH-] in the reaction mixture =100.00×10−3 =0.011 mol dm-3
 y = mx + c

Time/ s [OH-]/ mol dm-3 1/[OH-]/ mol-1dm3

120 0.019 52.63

300 0.018 55.55

600 0.016 62.50

900 0.0148 67.56

1200 0.0132 75.75

1500 0.012 83.33

1800 0.011 90.90

1/[OH-] vs Time
100
90
80
1/[OH-]/ mol-1dm3

70
60 y = 0.0229x + 48.748
50 R² = 0.9953
40
30
20
10
0
0 500 1000 1500 2000
time/s

Gradient = k2 = 0.0229

Second order rate constant according to the titration method = 0.0299 mol-1 dm3s-1
Conductance method

ln [G (t) – G (t + t)] = -k1t + constant

Each reading from 30 sec to 5min is paired with the corresponding reading 5 mins later, i.e.
30 s with 5 min 30 s; 1 min with 6 min etc.

Time / s G(t) / mS t+ t/s G(t + t) / mS G (t) – G (t + t) / mS ln [G(t) – G(t + t)]

30 921 330 461 460 6.31

60 831 360 468 363 5.89

90 771 390 448 323 5.77

120 713 420 411 302 5.70

150 665 450 410 255 5.54

180 613 480 425 188 5.23

210 578 510 436 142 4.95

240 538 540 437 101 4.61

270 488 570 433 55 4.00

300 456 600 432 24 3.17

ln [G(t) – G(t + t)] vs Time

7

6 y = -0.0101x + 6.7787
R² = 0.907
ln [G(t) – G(t +Δt)]

0
0 50 100 150 200 250 300 350
Time/s
Gradient = -k1 = -0.0101 s-1

k1 = 0.0101s-1

k1 = k2 [ester]0
5.00 1000
[ester] =0.05× 1000 ×10.00× 20.00 = 0.25 mol dm-3

0.0101= k2 × 0.25

k2 = 0.0404mol-1 dm3 s-1

Second order rate constant according to the conductance method = 0.0404 mol-1 dm3 s-1

Post Laboratory Questions :

(1) Second order rate constant according to the titration method = 0.0299 mol-1 dm3s-1

Second order rate constant according to the conductance method = 0.0404 mol-1 dm3 s-1

Literature value of the second order rate constant = 0.11 mol-1 dm3s-1
(experimental value−literature value)
Error percentage of titration method = literature value
×100

0.0299mol−1 dm3 s−1 − 0.11mol−1 dm3 s−1

=| 0.11mol−1 dm3 s−1
|

= 79.18%
(experimental value−literature value)
Error percentage of conductance method = ×100
literature value

0.0404 dm3 s−1 − 0.11mol−1 dm3 s−1

=| 0.11mol−1 dm3 s−1
|

= 63.27%

The conductance method is more accurate because it’s near to the literature value of the second
order rate constant of ethyl acetate hydrolysis than the titration method.

(2) If the concentrations of hydroxide solution and the ethyl acetate solution were slightly different it
does not affect the rate constant as the rate constant is independent of the concentration even
though the rate of the reaction depends on the concentration. The rate constant depends on the
temperature according to the Arrhenius equation.
𝐸𝑎
k = A𝑒 𝑅𝑇
Discussion :
In order to improve the reliability and to obtain information about the variability of results, two to five
portions (replicates) of a sample are usually carried through an entire analytical procedure. Sometimes
many different methods are used to determine the same physical quantity, but each method has its own
unique problems and errors and each method will give a slightly different answer.
Results can be precise without being accurate and accurate without being precise. Precision and accuracy
are two main factors that should be maintained in an experiment.
Experimental results are affected by at least two types of errors. One type, called random (or
indeterminate) error, causes data to be scattered more or less symmetrically around a mean value.
Repeating measurements will help to account for random errors. A second type of error, called systematic
(or determinate) error, causes the mean of a data set to differ from the accepted value.
In this experiment we consider two methods to determine the second order rate constant of the hydrolysis
of ethyl acetate. The hydrolysis can occur in the acidic medium where the acid acts as a catalyst and the
reaction is first order with respect to the ester and it can occur in the basic medium where the base unlike
the acid takes part in the reaction and the reaction is second order.
The first method is the titration method where the hydroxyl concentration is determined by a back titration.
There can be many errors associated with this method, like during the transfer of the reaction mixture in to
the flask containing HCl to quench the reaction, stopping the titration at the right color change, when
reading the titrate volume and also the delay in starting the stop watch as its done manually etc.
In the reaction mixture as the hydrolysis of the ester takes place acetate ions are formed. This acetate ions
will take up H+ from the HCl and form acetic acid. This acetic acid can also be titrated with the NaOH, as
Phenolphthalein is a good indicator for weak acid and strong base titration. Using BTB will be much more
suitable for the reaction between the strong acid and the strong base.
CH3COO- + H+ ⇋ CH3COOH

CH3COOH + NaOH → CH3COO- + H2O

Phenolphthalein pH range = 8.3 – 10.0

But the second reaction is not seen, since the NaOH reacts with HCl first which results in H+ being
continuously removed from the medium and the equilibrium of the reaction is more towards the left hand
side. Therefore acetic acid is formed less and less. Therefore we can assume that the base reacts only with
HCl.

As the rate constant depends on temperature it’s really important to maintain the temperature. Therefore
errors can also be caused due to the fluctuation from the equilibrium temperature in both the methods. A
very low temperature (5 ) is used in the case of the titration method to prevent the acid hydrolyzing the
ester. In very low temperature the hydrolysis of ester by the acid is hindered.

Conductance is the reciprocal of resistance. It measures the ability of electrolyte solution to conduct
electricity. It depends on the number of ions in solution and how mobile they are to make use the change in
conductance. In here, excess amount of ethyl acetate is used approximately 100 times higher than NaOH.
We can assume only NaOH participate the reaction and ethyl acetate doesn’t change the initial
concentration.

By considering the both methods the second order rate constant of alkaline hydrolysis of ethyl acetate is not
the same for the two methods mention in this experiment. Temperature variations, pressure variations,
measurement errors can be reasons for this differentiation as mention above.

Reference:

Physical chemistry; ninth edition; Peter Atkins; page826